CN107895809A

CN107895809A - Flow battery

Info

Publication number: CN107895809A
Application number: CN201710661779.5A
Authority: CN
Inventors: 成山穗奈美; 大冢友
Original assignee: Panasonic Intellectual Property Management Co Ltd
Current assignee: Panasonic Intellectual Property Management Co Ltd
Priority date: 2016-10-04
Filing date: 2017-08-04
Publication date: 2018-04-10
Also published as: JP2018060782A; US20180097247A1; US10547077B2

Abstract

It is expected to realize the flow battery with high discharge potential in the prior art.The disclosure provides a kind of flow battery, possesses：The 1st liquid dissolved with the 1st electrode amboceptor, the 1st electrode, the 1st cycling mechanism for being impregnated in the 1st active material of the 1st liquid and making the 1st liquid be circulated between the 1st electrode and the 1st active material for being impregnated in the 1st liquid, the 1st electrode amboceptor includes Tetrathiafulvalene Derivatives, the 4 of the tetrathiafulvalene skeleton of the Tetrathiafulvalene Derivatives, 5 and 4 ', 5 ' positions are bonded with substituent with ring style.

Description

Flow battery

Technical field

This disclosure relates to flow battery.

Background technology

Patent document 1 discloses a kind of redox flow battery system, and there is the energy containing redox mediators to deposit for it Reservoir.

Citation

Patent document 1：Japanese Unexamined Patent Application Publication 2014-524124 publications

The content of the invention

The invention solves problem

In the prior art, it is expected to realize the flow battery with high discharge potential.

The means to solve the problem

The flow battery of one embodiment of the disclosure, possesses：The 1st liquid dissolved with the 1st electrode amboceptor；It is impregnated in 1st electrode of the 1st liquid；It is impregnated in the 1st active material of the 1st liquid；And make the 1st liquid described The 1st cycling mechanism circulated between 1 electrode and the 1st active material, the 1st electrode amboceptor derive comprising tetrathiafulvalene Thing, at 4,5 and 4 ' of the tetrathiafulvalene skeleton of the Tetrathiafulvalene Derivatives, 5 ' positions are bonded substituted with ring style Base.

The effect of invention

According to the disclosure, the flow battery with high discharge potential can be realized.

Brief description of the drawings

Fig. 1 is the block diagram for the general configuration for representing the flow battery 1000 in embodiment 1.

Fig. 2 is the figure for representing can be used as the measurement result of the current potential of the Tetrathiafulvalene Derivatives of the 1st electrode amboceptor 111.

Fig. 3 is the schematic diagram for the general configuration for representing the flow battery 2000 in embodiment 2.

Fig. 4 is the block diagram for the general configuration for representing the flow battery 3000 in embodiment 3.

Fig. 5 is the figure for representing can be used as the current potential of the condensed aromatic compounds of group of charging amboceptor 121.

Fig. 6 is the figure for representing can be used as the current potential of the condensed aromatic compounds of group of electric discharge amboceptor 122.

Fig. 7 is the figure of the reckoning result for the energy density for representing the flow battery 3000 in embodiment 3.

Fig. 8 is the schematic diagram for the general configuration for representing the flow battery 4000 in embodiment 4.

Embodiment

Hereinafter, embodiment of the present disclosure is illustrated referring to the drawings.

(embodiment 1)

Flow battery 1000 in embodiment 1 possesses the 1st liquid 110, the 1st electrode 210, the 1st active material 310 and 1 cycling mechanism 510.

1st liquid 110 is the liquid dissolved with the 1st electrode amboceptor 111.

1st electrode 210 is the electrode for being impregnated in the 1st liquid 110.

1st active material 310 is the active material for being impregnated in the 1st liquid 110.

1st cycling mechanism 510 is the machine for making the 1st liquid 110 be circulated between the 1st electrode 210 and the 1st active material 310 Structure.

1st electrode amboceptor 111 includes Tetrathiafulvalene Derivatives.

At 4,5 and 4 ' of the tetrathiafulvalene skeleton of Tetrathiafulvalene Derivatives, 5 ' positions are bonded with ring style to be taken Dai Ji.

Technological maheup more than, can realize the circulation longevity with high discharge potential, high energy density and length The flow battery of life.

That is, the technological maheup more than, by 4,5 of the tetrathiafulvalene skeleton in Tetrathiafulvalene Derivatives and 4 ', 5 ' positions are bonded with the substituent (electron-withdrawing substituent) of ring-type, so as to be difficult to discharge electronics from Tetrathiafulvalene Derivatives.By This, with Tetrathiafulvalene Derivatives (such as the 3.2V vs.Li/Li without the substituent⁺Left and right) compare, can be further Improve charging potential and discharge potential.Therefore, even in using the high active material of equilibrium potential (such as 3.5V vs.Li/Li⁺ Left and right) it is electric with the balance closer to the 1st active material 310 as in the case of the 1st active material 310, can also realize The amboceptor of the discharge potential of position.Therefore, it is possible to realize the flow battery with higher discharge potential.

In addition, the technological maheup more than, can be realized using active material, and active material is circulated in itself Structure flow battery.Therefore, as the 1st active material 310, such as the powder of high power capacity in discharge and recharge reaction can be used Active material.Thereby, it is possible to realize high energy density and high capacity.

In addition, the technological maheup more than, can not be such that powder activity material circulates in itself, only make dissolved with the 1st electricity 1st liquid 110 of pole amboceptor 111 circulates.Situations such as therefore, it is possible to suppress the blocking of pipe arrangement etc. as caused by powder activity material Generation.Therefore, it is possible to realize the flow battery having extended cycle life.

Furthermore in the flow battery 1000 of embodiment 1, Tetrathiafulvalene Derivatives can be by following formulas (1) The Tetrathiafulvalene Derivatives of expression.

In formula (1), X is oxygen atom, sulphur atom, nitrogen-atoms, selenium atom or tellurium atom.Also, R₁And R₂Independently Ground be selected from chain saturated hydrocarbons, chain unsaturated hydrocarbons, cyclic saturated hydrocarbon, ring-type unsaturated hydrocarbons, oxygen atom, sulphur atom, nitrogen-atoms, Selenium atom, tellurium atom at least one of.

Technological maheup more than, the flow battery with higher discharge potential can be realized.

Furthermore hydrocarbon can include selected from oxygen atom, nitrogen-atoms, sulphur atom, silicon atom etc. at least one of.

In addition, in the flow battery 1000 of embodiment 1, the Tetrathiafulvalene Derivatives that are represented by formula (1) can be with Be bonded with X position selected from sulphur atom, nitrogen-atoms, oxygen atom at least one of electron withdraw group.

Technological maheup more than, by the presence of electron-withdrawing atoms, it can realize with higher discharge potential Flow battery.In the case of being particularly bonded with sulphur atom in X position, the liquid stream with higher discharge potential can be realized Battery.

In addition, in the flow battery 1000 of embodiment 1, the Tetrathiafulvalene Derivatives that are represented by formula (1) can be with In R₁And R₂Position possess the substituent of straight-chain.

In addition, in the flow battery 1000 of embodiment 1, in the Tetrathiafulvalene Derivatives represented by formula (1), R₁And R₂Position bonding substituent can be C_nH_2n(n is the integer of satisfaction 1≤n≤4).

Technological maheup more than, the flow battery with higher discharge potential can be realized.In addition, it can suppress Rise in the Tetrathiafulvalene Derivatives (situation that particularly substituent is only made up of chain saturated hydrocarbons) of n >=5 with fusing point And the situation of the deliquescent reduction occurred.That is, as in R₁And R₂Position bonding substituent, by using possess- CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂- the Tetrathiafulvalene Derivatives waited, can suppress for the 1st liquid 110 deliquescent reduction.

In addition, in the flow battery 1000 of embodiment 1, Tetrathiafulvalene Derivatives can be by following formulas (2) The Tetrathiafulvalene Derivatives of expression.

Wherein, R₃、R₄、R₅And R₆It is separately selected from chain saturated hydrocarbons, chain unsaturated hydrocarbons, cyclic saturated hydrocarbon, ring Shape unsaturated hydrocarbons, oxygen atom, sulphur atom, nitrogen-atoms, selenium atom or tellurium atom at least one of.In addition, on R₁、R₂With X, the structure same with above-mentioned formula (1) can be used.

The Tetrathiafulvalene Derivatives represented by formula (2), as in R₁And R₂Position bonding substituent, possess There is the substituent of side chain.

In addition, in the flow battery 1000 of embodiment 1, by formula (1) or the Tetrathiafulvalene Derivatives of (2) expression In, in R₁And R₂Position bonding substituent, can include selected from boron, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, among iodine More than one elements (nonmetalloid).

In addition, in the flow battery 1000 of embodiment 1, Tetrathiafulvalene Derivatives can be selected from 4,5,4 ', 5 '- Double (sulphur of methylene two) tetrathiafulvalenes, 4,5,4 ', 5 '-bis- (ethylene sulphur) tetrathiafulvalenes, 4,5,4 ', 5 '-bis- (Sanyas At least one of the sulphur of methyl two) tetrathiafulvalene

Prepare the electrolyte (LiBF for making 1M₄) it is dissolved in the electrolyte in the propylene carbonate as solvent.By by 1mM Fig. 2 shown in each compound be dissolved separately in the electrolyte, obtain it is corresponding with each compound phase shown in Fig. 2 electrolysis Liquid.By each electrolyte, to electrode (1 × 1cm Pt paper tinsels), working electrode (electrochemical gaging with glassy carbon electrode (φ 6mm)) With reference electrode (silver wire (Ag/Ag⁺)), make potential measurement element cell corresponding with each compound phase shown in Fig. 2. Using each potential measurement element cell, determined by cyclic voltammetric (CV), determine the discharge and recharge of each compound shown in Fig. 2 Current potential.The charge and discharge potential for showing to be determined in Fig. 2 is with current potential (V vs.Li/Li obtained from lithium metal basis conversion⁺)。

The oxysome of tetrathiafulvalene and its derivative shows aromatic character, and two stage redox reaction is presented.Cause This, tetrathiafulvalene and its derivative individually a kind of can be used as charge and discharge dielectric.The redox reaction of first stage is put down Weigh current potential (the 1st oxidation-reduction potential：E1(V vs.Li/Li⁺)) as the current potential of electric discharge amboceptor.The redox of second stage Equilibrium potential (the 2nd oxidation-reduction potential of reaction：E2(V vs.Li/Li⁺)) as the current potential of charging amboceptor.

Among each compound shown in Fig. 2, the Tetrathiafulvalene Derivatives in above-mentioned embodiment 1 (have ring-type The Tetrathiafulvalene Derivatives of substituent) being 4,5,4 ', 5 ' ,-bis- (sulphur of methylene two) tetrathiafulvalenes, 4,5,4 ', 5 '-are bis- (sub- The sulphur of ethyl two) tetrathiafulvalene, 4,5,4 ', 5 '-bis- (sulphur of trimethylene two) tetrathiafulvalenes, with the substituent without ring-type Tetrathiafulvalene compare, the 1st oxidation-reduction potential E1 (discharge potential) is higher.

The discharge potential of flow battery depends on the current potential of the electric discharge amboceptor of side of the positive electrode.Therefore, as long as than without The tetrathiafulvalene (with discharge potential near 3.2V) of the substituent of ring-type is by hot side with discharge potential, above-mentioned Tetrathiafulvalene Derivatives (Tetrathiafulvalene Derivatives with the substituent of ring-type) in embodiment 1, it becomes possible to realize Flow battery with higher discharge potential.

Furthermore in the flow battery 1000 of embodiment 1, the 1st electrode amboceptor 111, which can be included only, meets above-mentioned implementation A kind of Tetrathiafulvalene Derivatives of the condition of Tetrathiafulvalene Derivatives in mode 1.

Or in the flow battery 1000 of embodiment 1, the 1st electrode amboceptor 111, which can include, meets above-mentioned embodiment party The two or more Tetrathiafulvalene Derivatives of the condition of Tetrathiafulvalene Derivatives in formula 1.

As described above, the Tetrathiafulvalene Derivatives in embodiment 1 have the oxidations of the 1st oxidation-reduction potential E1 and the 2nd Reduction potential E2.

Now, equilibrium potential (the V vs.Li/Li of the 1st active material 310⁺) can be higher than the 1st oxidation-reduction potential E1, It is and lower than the 2nd oxidation-reduction potential E2.

Technological maheup more than the, by using (display with the equilibrium potential higher than the 1st oxidation-reduction potential E1 The current potential higher than the 1st oxidation-reduction potential E1) active material as the 1st active material 310, can make in embodiment 1 Tetrathiafulvalene Derivatives play a role as electric discharge amboceptor.In addition, by using with lower than the 2nd oxidation-reduction potential E2 (showing the current potential lower than the 2nd oxidation-reduction potential E2) active material of equilibrium potential uses as the 1st active material 310, The Tetrathiafulvalene Derivatives in embodiment 1 can be made to be played a role as charging amboceptor.

In addition, in the flow battery 1000 of embodiment 1, the 1st active material 310 can be by Li_xM_yO₂The gold of expression Belong to oxide.Wherein, M be selected from Ni, Mn, Co at least one of.X and y is arbitrarily to be worth.The metal oxide is 3.2 ~3.8V has equilibrium potential.

In addition, in the flow battery 1000 of embodiment 1, the 1st active material 310 can be selected from LiFePO₄、 LiMnO₂、LiMn₂O₄、LiCoO₂At least one of.

Here, LiFePO₄Equilibrium potential be 3.5V vs.Li/Li⁺.Now, if using than LiFePO₄Balance The high current potential of current potential has discharge potential and than LiFePO₄The low current potential of equilibrium potential there is the chemical combination of charging potential Thing can be then formed with LiFePO as the 1st electrode amboceptor 111 (discharge and recharge amboceptor)₄For active material mediator type just Pole.Now, LiFePO₄Equilibrium potential and the potential difference of the charge and discharge current potential of the 1st electrode amboceptor 111 it is fewer, charge-discharge energy effect Rate is better.For example, the discharge potential in the 1st electrode amboceptor 111 compares LiFePO₄Equilibrium potential it is low and closer to LiFePO₄ Equilibrium potential in the case of, the discharge potential of flow battery is higher.

Therefore, LiFePO is being used₄In the case of as the 1st active material 310, by using 4,5,4 ', 5 '-bis- (sub- Methyl two is thio) tetrathiafulvalene, 4,5,4 ', 5 '-bis- (ethylene is thio) tetrathiafulvalenes, 4,5,4 ', 5 '-bis- (Sanyas Methyl two is thio) tetrathiafulvalene as the 1st electrode amboceptor 111, can further improve the discharge potential of flow battery.That is, In this case, with using the tetrathiafulvalene (there is discharge potential near 3.2V) for the substituent for not having ring-type to be used as the 1st The situation of electrode amboceptor 111 is compared, it is possible to increase discharge potential about 0.1~0.3V or so.

Furthermore as the 1st active material 310, the active material (such as powdered active material) of solid can be used. In the case where the 1st active material 310 is filled into tank with the pulverulence not being processed, manufacture can be simplified, And reduce manufacturing cost.

Or as the 1st active material 310, the active matter of graininess (such as state by granulating powders) can be used Matter.By the 1st active material 310 with particulate filler into tank in the case of, manufacture can be simplified, and reduce be manufactured into This.

Or as the 1st active material 310, it can use by generally known adhesive (such as poly- inclined difluoro second Alkene, polypropylene, polyethylene, polyimides etc.) form granular active material.

Furthermore the 1st active material 310 can be the material for being not dissolved in the 1st liquid 110.Thereby, it is possible to realize to make the 1st Electrode amboceptor 111 circulates together with the 1st liquid 110, but the flow battery of structure that the 1st active material 310 does not circulate.

In addition, in the flow battery 1000 of embodiment 1, the 1st liquid 110 can be selected from propylene carbonate (PC), Among ethylene carbonate (EC), gamma-butyrolacton, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) At least one.

In addition, in the flow battery 1000 of embodiment 1, the 1st liquid 110 can will can be used as above-mentioned 1st liquid 110 material as solvent, include electrolyte solution.The electrolyte (salt) can be selected from LiBF₄、LiPF₆、LiN (CF₃SO₂)₂At least one of.In addition, the solvent can be dielectric constant height, and it is reactive low with Li ions, and And solvent of the potential window near 4V.

Furthermore in the flow battery 1000 of embodiment 1, it is positive pole that can be set to the 1st electrode 210, and the 2nd electrode 220 be negative pole.

Furthermore if using the relatively high electrode of current potential as the 2nd electrode 220, the 1st electrode 210 can also turn into negative pole.

I.e., it is possible to which it is negative pole to be set to the 1st electrode 210, and the 2nd electrode 220 is positive pole.

Furthermore contacted in the flow battery 1000 of embodiment 1, such as by the 1st liquid 110 with the 1st electrode 210, The 1st electrode amboceptor 111 is set to be aoxidized or be reduced by the 1st electrode 210.

1st electrode 210 can be the electrode on the surface to be played a role with the reacting field as the 1st electrode amboceptor 111.

In this case, as the 1st electrode 210, can be used for the stable material of the 1st liquid 110 (such as insoluble in the 1st The material of liquid 110).In addition, as the 1st electrode 210, can be used for electrode reaction is the stable material of electrochemical reaction. For example, as the 1st electrode 210, metal (stainless steel, iron, copper, nickel etc.), carbon etc. can be used.

1st electrode 210 can be increase its surface area structure (such as silk screen, non-woven fabrics, surface roughening plate, Sintered porous bodies etc.).So, the specific surface area increase of the 1st electrode 210.Thereby, it is possible to be easier to make for the 1st electrode amboceptor 111 Oxidation reaction or reduction reaction.

2nd electrode 220 can be the structure for possessing collector and setting active material on the current collector.Thus, such as The active material of high power capacity can be used.As the active material of the 2nd electrode 220, can be used has reversibly occlusion and discharges The compound of the characteristic of lithium ion.

Or the 2nd electrode 220 can be lithium metal.In the case where using lithium metal as the 2nd electrode 220, easily control The solution modeling of metal positive-pole is made as, and high power capacity can be realized.

Furthermore the flow battery 1000 in embodiment 1 can be also equipped with isolation part 400.

Isolation part 400 will keep apart between the 1st electrode 210 and the 1st liquid 110 and the 2nd electrode 220.

Isolation part 400 can be micro-porous film (porous body) used in known secondary cell.

Or isolation part 400 can be into perforated membranes such as the glassine papers of non-woven fabrics by fiberglass braided.

Or isolation part 400 can be the barrier film for having ionic conductivity (lithium-ion-conducting).For example, isolation part 400 Can be ion exchange resin membrane (such as cation-exchange membrane, anion-exchange membrane etc.) or solid electrolyte film etc..

Technological maheup more than, can make the 1st electrode amboceptor 111 together with the 1st liquid 110 the 1st electrode 210 with Circulated between 1st active material 310.Thereby, it is possible to efficiently carry out oxidation reaction and reduction reaction between each material.

Mechanism of 1st cycling mechanism 510 such as can be to possess pipe arrangement, tank, pump, valve.

As specific one of the 1st cycling mechanism 510, structure of embodiment 2 described later etc. can be enumerated.

The explanation ＞ of ＜ charge and discharge process

Hereinafter, the charge and discharge process of the flow battery 1000 in embodiment 1 is illustrated.

In addition, specifically, following technological maheups i.e. operational instances are exemplified, charge and discharge process is illustrated.

That is, in this operational instances, the 1st electrode 210 is positive pole, is set to carbon black.

In addition, in this operational instances, the 1st liquid 110 is set to the ethereal solution dissolved with the 1st electrode amboceptor 111.

In addition, in this operational instances, the tetrathiafulvalene that the 1st electrode amboceptor 111 is set to above-mentioned embodiment 1 derives Thing (is designated as TTF) below.

In addition, in this operational instances, the 1st active material 310 is set to LiFePO4 (LiFePO₄)。

In addition, in this operational instances, the 2nd electrode 220 is negative pole, is set to lithium metal.

[explanation of charging process]

First, charging reaction is illustrated.

By to applying voltage between the 1st electrode 210 and the 2nd electrode 220, being charged.

(reaction of negative side)

By the application of voltage, electronics is supplied from the outside of flow battery to the 2nd electrode 220 as negative pole.Thus, exist Reduction reaction occurs for the 2nd electrode 220 as negative pole.That is, negative pole turns into charged state.

For example, in this operational instances, following reactions occur.

Li⁺+e^-→Li

(reaction of side of the positive electrode)

By the application of voltage, the oxidation reaction of the 1st electrode amboceptor 111 occurs in the 1st electrode 210 as positive pole.That is, On the surface of the 1st electrode 210, the 1st electrode amboceptor 111 is oxidized.Thus, the outside release from the 1st electrode 210 to flow battery Electronics.

For example, in this operational instances, following reactions occur.

TTF→TTF⁺+e^-

TTF⁺→TTF²⁺+e^-

By the 1st cycling mechanism 510, make to move (supply) to setting by the 1st oxidized electrode amboceptor 111 of the 1st electrode 210 It is equipped with the place of the 1st active material 310.

Now, the 1st electrode amboceptor 111 being oxidized on the 1st electrode 210, reduced by the 1st active material 310.That is, 1st active material 310 is aoxidized by the 1st electrode amboceptor 111.Thus, the 1st active material 310 discharges lithium.

For example, in this operational instances, following reactions occur.

LiFePO₄+TTF²⁺→FePO₄+Li⁺+TTF⁺

By the 1st cycling mechanism 510, make to be moved (supply) by the 1st electrode amboceptor 111 that the 1st active material 310 reduces To the place for being provided with the 1st electrode 210.

Now, it is oxidized in the surface of the 1st electrode 210, the 1st electrode amboceptor 111.

For example, in this operational instances, following reactions occur.

TTF⁺→TTF²⁺+e^-

Furthermore caused lithium ion (Li⁺) a part can from isolation part 400 by, to the side of the 2nd electrode 220 move.

As described above, from the point of view of the 1st electrode amboceptor 111 is with the overall reaction including circulation, do not change.

On the other hand, the 1st active material 310 in the place of the 1st electrode 210 is located remotely from, turns into charged state.

As described above, in the side of the 1st electrode 210, TTF⁺As charging amboceptor (charge amboceptor for the 1st electrode side).

Under fully charged state, TTF be present in the 1st liquid 110²⁺, the 1st active material 310 turns into FePO₄.Now, fill Electric potential is to TTF²⁺Oxidizing potential determine.

More than charging reaction may proceed to the 1st active material 310 as fully charged state or the 2nd electrode 220 into Untill fully charged state.

[explanation of discharge process]

Below, the exoelectrical reaction since full charge is illustrated.

In the case of full charge, the 1st active material 310 and the 2nd electrode 220 turn into charged state.

In exoelectrical reaction, electric power is taken out between the 1st electrode 210 and the 2nd electrode 220.

(reaction of negative side)

Oxidation reaction occurs in the 2nd electrode 220 as negative pole.That is, negative pole turns into discharge condition.Thus, from the 2nd electrode 220 discharge electronics to the outside of flow battery.

For example, in this operational instances, following reactions occur.

Li→Li⁺+e^-

(reaction of side of the positive electrode)

By the electric discharge of battery, electronics is supplied from the outside of flow battery to the 1st electrode 210 as positive pole.Thus, exist On 1st electrode 210, the reduction reaction of the 1st electrode amboceptor 111 occurs.That is, in the surface of the 1st electrode 210, the 1st electrode amboceptor 111 are reduced.

For example, in this operational instances, following reactions occur.

TTF²⁺+e^-→TTF⁺

TTF⁺+e^-→TTF

By the 1st cycling mechanism 510, make to move (supply) to setting by the 1st electrode amboceptor 111 that the 1st electrode 210 reduces It is equipped with the place of the 1st active material 310.

Now, the 1st electrode amboceptor 111 being reduced on the 1st electrode 210, aoxidized by the 1st active material 310.That is, 1st active material 310 is reduced by the 1st electrode amboceptor 111.Thus, the 1st active material 310 absorbs lithium.

For example, in this operational instances, following reactions occur.

FePO₄+Li⁺+TTF→LiFePO₄+TTF⁺

By the 1st cycling mechanism 510, make to be moved (supply) by the 1st oxidized electrode amboceptor 111 of the 1st active material 310 To the place for being provided with the 1st electrode 210.

Now, it is reduced in the surface of the 1st electrode 210, the 1st electrode amboceptor 111.

For example, in this operational instances, following reactions occur.

TTF⁺+e^-→TTF

Furthermore lithium ion (Li⁺) a part can from isolation part 400 by, from the side of the 2nd electrode 220 supply.

On the other hand, being located remotely from the 1st active material 310 in the place of the 1st electrode 210 turns into discharge condition.

As described above, in the side of the 1st electrode 210, TTF turns into electric discharge amboceptor (discharge amboceptor for the 1st electrode side).

Under complete discharge condition, TTF in the 1st liquid 110 be present, the 1st active material 310 turns into LiFePO₄.Now, Discharge potential to TTF reduction potential from determining.

More than exoelectrical reaction may proceed to the 1st active material 310 as complete discharge condition or the 2nd electrode 220 into Untill complete discharge condition.

(embodiment 2)

Hereinafter, embodiment 2 is illustrated.It is furthermore appropriate to omit the explanation repeated with above-mentioned embodiment 1.

Flow battery 2000 in embodiment 2, except the flow battery 1000 in above-mentioned embodiment 1 structure with Outside, following structures are also equipped with.

That is, in the flow battery 2000 in embodiment 2, the 1st cycling mechanism 510 possesses the 1st receiving portion 511.

1st active material 310 and the 1st liquid 110 are accommodated in the 1st receiving portion 511.

1st cycling mechanism 510 makes the 1st liquid 110 be circulated between the 1st electrode 210 and the 1st receiving portion 511.

In the 1st receiving portion 511, the 1st active material 310 contacts with the 1st liquid 110, thus carries out by the 1st active material At least one of the oxidation reaction of 1st electrode amboceptor 111 caused by 310 and reduction reaction.

Technological maheup more than, in the 1st receiving portion 511, can make the 1st liquid 110 and the 1st active material 310 Contact.Thus, such as the contact area of the 1st liquid 110 and the 1st active material 310 can further be increased.In addition, it can enter One step extends the time of contact of the 1st liquid 110 and the 1st active material 310.Therefore, it is possible to efficiently carry out by the 1st activity The oxidation reaction and reduction reaction of 1st electrode amboceptor 111 caused by material 310.

Furthermore in embodiment 2, the 1st receiving portion 511 for example can be tank.

In addition, the 1st receiving portion 511 can for example accommodate in the gap for the 1st active material 310 filled and be dissolved with the 1st 1st liquid 110 of electrode amboceptor 111.

In addition, as shown in figure 3, the flow battery 2000 in embodiment 2 can be also equipped with electrochemical reaction portion 600, just Extreme son 211 and negative terminal 221.

Electrochemical reaction portion 600 is isolated portion 400 and is divided into cathode chamber 610 and anode chamber 620.

The electrode (being the 1st electrode 210 in the example shown in Fig. 3) of positive pole is configured as in cathode chamber 610.

Positive terminal 211 is connected with as the electrode of positive pole.

The electrode (being the 2nd electrode 220 in the example shown in Fig. 3) of negative pole is configured as in anode chamber 620.

Negative terminal 221 is connected with as the electrode of negative pole.

Positive terminal 211 and negative terminal 221 are for example connected with charge and discharge device.By charge and discharge device, to positive terminal Apply voltage between son 211 and negative terminal 221, or electric power is taken out between positive terminal 211 and negative terminal 221.

In addition, as shown in figure 3, in the flow battery 2000 of embodiment 2, the 1st cycling mechanism 510 can possess pipe arrangement 514th, pipe arrangement 513 and pump 515.

One end of pipe arrangement 514 is with configuring one of the 1st electrode 210 (shown in Fig. 3 among cathode chamber 610 and anode chamber 620 Example in be cathode chamber 610) connection.

The other end of pipe arrangement 514 is connected with the inflow entrance side of the 1st liquid 110 of the 1st receiving portion 511.

One end of pipe arrangement 513 is connected with the flow export side of the 1st liquid 110 of the 1st receiving portion 511.

The other end of pipe arrangement 513 is with configuring one of the 1st electrode 210 (in Fig. 3 institutes among cathode chamber 610 and anode chamber 620 It is cathode chamber 610 in the example shown) connection.

Pump 515 is for example arranged at pipe arrangement 514.Or pump 515 can be arranged at pipe arrangement 513.

Furthermore in the flow battery 2000 of embodiment 2, the 1st cycling mechanism 510 can possess the 1st and pass through suppressing portion 512。

1st suppresses the transmission of the 1st active material 310 through suppressing portion 512.

1st is arranged at the path that the 1st liquid 110 flows out from the 1st receiving portion 511 to the 1st electrode 210 through suppressing portion 512 (being pipe arrangement 513 in the example shown in Fig. 3).

Technological maheup more than, the 1st active material 310 can be suppressed to (such as the 1st electricity beyond the 1st receiving portion 511 The side of pole 210) place outflow.That is, the 1st active material 310 stays in the 1st receiving portion 511.Thereby, it is possible to realize not make the 1st activity The flow battery of the structure of material 310 circulation itself.Therefore, it is possible to prevent the part (such as pipe arrangement) of the 1st cycling mechanism 510 Inside occurs to block caused by the 1st active material 310.In addition, it can prevent because the 1st active material 310 is to the side of the 1st electrode 210 The generation of ohmic loss caused by outflow.

1st can for example be arranged at the 1st receiving portion 511 and the junction surface of pipe arrangement 513 through suppressing portion 512.

1st transmission suppressing portion 512 for example can be the filter for filtering the 1st active material 310.Now, filter can Be the particle with than the 1st active material 310 the small hole of minimum grain size part.As the material of filter, can be used Not with the 1st active material 310 and the material of the grade reaction of the 1st liquid 110.Filter for example can be glass fiber filter paper, poly- third Alkene non-woven fabrics, not polyethylene nonwoven, the wire netting etc. with lithium metal reaction.

Technological maheup more than, in the inside of the 1st receiving portion 511, even if occurring with the flowing of the 1st liquid 110 The flowing of 1st active material 310, also it can prevent the 1st active material 310 from being flowed out from the 1st receiving portion 511.

In the example shown in Fig. 3, the 1st liquid 110 of the 1st receiving portion 511 is contained in, the He of suppressing portion 512 is passed through the 1st By supplying to cathode chamber 610 in pipe arrangement 513.

Thus, the 1st electrode amboceptor 111 of the 1st liquid 110 is dissolved in, is aoxidized or is reduced by the 1st electrode 210.

Then, the 1st liquid 110 dissolved with the 1st electrode amboceptor 111 being oxidated or reduced, in pipe arrangement 514 and pump By supplying to the 1st receiving portion 511 in 515.

Thus, to being dissolved in the 1st electrode amboceptor 111 of the 1st liquid 110, carry out the 1st as caused by the 1st active material 310 At least one of the oxidation reaction of electrode amboceptor 111 and reduction reaction.

Furthermore the control of the circulation of the 1st liquid 110, such as can be carried out by pump 515.That is, suitably entered by pump 515 Beginning, the stopping of supply or the adjustment of quantity delivered etc. of the supply of the liquid 110 of row the 1st.

Or the 1st liquid 110 circulation control, can be entered by the other means (such as valve etc.) different from pump 515 OK.

Furthermore it is positive pole labeled as the 1st electrode 210 in figure 3, as one, and the 2nd electrode 220 is negative pole.

If here, using the relatively high electrode of current potential as the 2nd electrode 220, the 1st electrode 210 can also turn into negative pole.

Furthermore can be different using forming respectively in the side of cathode chamber 610 and the side of anode chamber 620 across isolation part 400 Electrolyte (solvent).

Or composition identical electrolyte (solvent) can be used in the side of cathode chamber 610 and the side of anode chamber 620.

(embodiment 3)

Hereinafter, embodiment 3 is illustrated.In addition, appropriate omit and above-mentioned embodiment 1 or the weight of embodiment 2 Multiple explanation.

As embodiment 3, the structure for circulating electrolyte in both the 1st electrode side and the 2nd electrode side is shown.

Flow battery 3000 in embodiment 3 is except possessing the knot of the flow battery 1000 in above-mentioned embodiment 1 Beyond structure, following structures are also equipped with.

That is, the flow battery 3000 in embodiment 3 is also equipped with the 2nd liquid 120, the 2nd electrode 220, the 2nd active material 320 and isolation part 400.

2nd liquid 120 is dissolved with charging amboceptor 121 (charge amboceptor for the 2nd electrode side) and electric discharge (the 2nd electrode of amboceptor 122 Side discharge amboceptor) liquid.

2nd electrode 220 is the electrode for being impregnated in the 2nd liquid 120.

2nd active material 320 is the active material for being impregnated in the 2nd liquid 120.

Isolation part 400 will keep apart between the 1st electrode 210 and the 1st liquid 110 and the 2nd electrode 220 and the 2nd liquid 120.

The equilibrium potential of charging amboceptor 121 is lower than the equilibrium potential of the 2nd active material 320.

The equilibrium potential of electric discharge amboceptor 122 is higher than the equilibrium potential of the 2nd active material 320.

Technological maheup more than, it can realize with higher cell voltage, higher energy density and longer The flow battery of cycle life.

That is, the technological maheup more than, by using equilibrium potential (vs.Li/Li⁺) relatively low active material (such as Graphite) the 2nd active material 320 is used as, equilibrium potential (vs.Li/Li can be used⁺) relatively low material (such as fused aromatic Compound) as electric discharge amboceptor 122.Thereby, it is possible to realize the negative pole of the lower flow battery of current potential.Therefore, it is possible to realize tool There is the flow battery of higher cell voltage (discharge voltage).

In addition, the technological maheup more than, can realize using active material and active material is circulated in itself Structure flow battery.Therefore, as the 2nd active material 320, such as the powder that capacity is high in discharge and recharge reaction can be used Last active material.Thereby, it is possible to realize high-energy-density and high power capacity.

In addition, the technological maheup more than, can not be such that powder activity material circulates in itself, only make to be situated between dissolved with charging 2nd liquid 120 of body 121 and electric discharge amboceptor 122 circulates.Therefore, it is possible to suppress pipe arrangement etc. as caused by powder activity material The generation of situations such as blocking.So as to realize the flow battery having extended cycle life.

Furthermore in the flow battery 3000 of embodiment 3, lithium can be dissolved with the 2nd liquid 120.

2nd active material 320 can be the material of the property with occlusion and release lithium.

It can be set to, (be supplied in the charging of flow battery 3000 from the outside of flow battery 3000 to the 2nd electrode 220 The state of electron), charging amboceptor 121 is reduced on the 2nd electrode 220, also, the charging being reduced on the 2nd electrode 220 Amboceptor 121 is aoxidized by the 2nd active material 320, while the 2nd active material 320 absorbs lithium.

It can be set to, (be released in the electric discharge of flow battery 3000 from the outside of the 2nd electrode 220 to flow battery 3000 The state of electric discharge), the 2nd active material 320 for having absorbed lithium reduces electric discharge amboceptor 122, while the 2nd active material 320 is released Lithium is released, also, the electric discharge amboceptor 122 reduced by the 2nd active material 320 is oxidized on the 2nd electrode 220.

Technological maheup more than, as the 2nd active material 320, such as it can use to have and reversibly absorb and release Put the active material of the property of lithium (such as lithium ion).Thus, the design of material of the 2nd active material 320 becomes easier to.Separately Outside, higher capacity can be realized.

In addition, in the flow battery 3000 of embodiment 3, in charging, electric discharge amboceptor 122 can be in the 2nd electrode 220 On be reduced.

In addition, in electric discharge, charging amboceptor 121 can be oxidized on the 2nd electrode 220.

Technological maheup more than, can realize higher energy density and Geng Gao capacity.That is, pass through in charging 2nd electrode 220 reduces electric discharge amboceptor 122, thus enables that the electric discharge amboceptor 122 that aoxidized in electric discharge by the 2nd electrode 220 Amount increase.In addition, being aoxidized charging amboceptor 121 by the 2nd electrode 220 in electric discharge, thus enabling that will quilt in charging The amount increase of the charging amboceptor 121 of 2nd electrode 220 reduction.So as to increase the capacity of discharge and recharge.

In addition, in the flow battery 3000 of embodiment 3, charging amboceptor 121 and electric discharge amboceptor 122 can be fusion virtues Fragrant compounds of group.

The 2nd liquid 120 dissolved with condensed aromatic compounds of group have discharge the solvated electron of lithium, by lithium with The property of cationic form dissolving.

Technological maheup more than, charging amboceptor 121 and electric discharge amboceptor with the low property of current potential can be realized 122.Solution (such as ethereal solution) containing condensed aromatic compounds of group has the ability of dissolving lithium (such as lithium metal).Lithium is easy Discharge electronics and turn into cation.Therefore, the condensed aromatic compounds of group into solution transmits electronics, turns into cation and dissolves In the solution.Now, receive electronics condensed aromatic compounds of group and solvation occurs with electronics.By with electron donor solvent, it is thick Close the form that aromatic compound shows as anion.Therefore, the solution containing condensed aromatic compounds of group has ion in itself Electric conductivity.Here, in the solution containing condensed aromatic compounds of group, Li cations and electronics equivalent are present.Therefore, it is possible to make Solution containing condensed aromatic compounds of group has strong (low in other words as the current potential) property of reproducibility in itself.

If for example, the electrode not with lithium reaction is impregnated in the 2nd liquid 120 dissolved with condensed aromatic compounds of group In, the current potential of measure and lithium metal, then observe low-down current potential.Observed current potential depends on condensed aromatic compounds of group With the degree (i.e. the species of condensed aromatic compounds of group) of the solvation of electronics.As the fused aromatic for producing low current potential Compound, phenanthrene, biphenyl, ortho-terphenyl, Sanya phenyl, anthracene, phenanthroline, 2,2 '-bipyridyl, benzophenone, trans hexichol can be enumerated Ethene, 4,4 '-bipyridyl, 3,3 '-bipyridyl, 2,4 '-bipyridyl, 2,3 '-bipyridyl, cis-stilbene, acetophenone, phenylpropyl alcohol Ketone, phenyl propyl ketone, benzene pentanone, ethylenediamine etc..

In addition, in the flow battery 3000 of embodiment 3, charging amboceptor 121 can be selected from phenanthrene, biphenyl, neighbour three Biphenyl, Sanya phenyl, anthracene at least one of.

Technological maheup more than, can realize the charging amboceptor 121 with the low property of current potential.More specifically, Current potential (the vs.Li/Li shown than specific 2nd active material 320 (such as graphite) can be realized⁺) low current potential (vs.Li/Li⁺) charging amboceptor.

In addition, in the flow battery 3000 of embodiment 3, electric discharge amboceptor 122 can be selected from phenanthroline, 2,2 '-connection It is pyridine, benzophenone, trans stilbene, 4,4 '-bipyridyl, 3,3 '-bipyridyl, 2,4 '-bipyridyl, 2,3 '-bipyridyl, suitable At least one of formula talan, acetophenone, propiophenone, phenyl propyl ketone, benzene pentanone, ethylenediamine.

Technological maheup more than, can realize the electric discharge amboceptor 122 with the high property of current potential.More specifically, Current potential (the vs.Li/Li shown than specific 2nd active material 320 (such as graphite) can be realized⁺) high current potential (vs.Li/Li⁺) electric discharge amboceptor 122.

In addition, in the flow battery 3000 of embodiment 3, electric discharge amboceptor 122 can be 2,2 '-bipyridyl, hexichol second Among alkene, 2,4 '-bipyridyl, 2,3 '-bipyridyl, cis-stilbene, propiophenone, phenyl propyl ketone, benzene pentanone, ethylenediamine at least It is a kind of

Technological maheup more than, the equilibrium potential (vs.Li/Li of electric discharge amboceptor 122 can be made⁺) relatively low.Thus, energy Enough realize the negative pole of the lower flow battery of current potential.Therefore, it is possible to realize the liquid with higher cell voltage (discharge voltage) Galvanic battery.

In addition, in the flow battery 3000 of embodiment 3, the 2nd liquid 120 can be ethereal solution.

Technological maheup more than, as the 2nd liquid 120, it can realize containing charging amboceptor 121 and electric discharge amboceptor 122 electrolyte.That is, because the solvent of charging amboceptor 121 and the amboceptor 122 that discharges is the ethereal solution without electron conduction, Therefore the ethereal solution can have the property as electrolyte in itself.

As ether, can be used tetrahydrofuran (THF), 2- methyltetrahydrofurans (2MeTHF), dimethoxy-ethane (DME), 1,3- bis-Alkane (1,3DO), 4- methyl isophthalic acids, 3- bis-Alkane (4Me1,3DO) etc..

In addition, in the flow battery 3000 of embodiment 3, the 2nd active material 320 can be graphite.

Technological maheup more than, the equilibrium potential (vs.Li/Li of the 2nd active material 320 can be made⁺) relatively low.Cause This, as electric discharge amboceptor 122, can use equilibrium potential (vs.Li/Li⁺) relatively low material (such as fused aromatic chemical combination Thing).Thereby, it is possible to realize the negative pole of the lower flow battery of current potential.Therefore, it is possible to realize with high cell voltage (electric discharge Voltage) flow battery.

Furthermore in embodiment 3, as the 2nd active material 320, the graphite for having absorbed lithium (generates in charging Compound between graphite layers) composition can be C₂₄Li、C₁₈Li、C₁₂Li、C₆At least one of Li.

As the 2nd active material 320, graphite (C is used₆Li in the case of), react with lithium and be reduced completely, filled Electricity (absorbs lithium and turns into C₆Li).Now, the C₆Li current potential is 0.2V vs.Li/Li⁺Left and right.Therefore, if using display Compare C₆The condensed aromatic compounds of group of the low current potential of Li current potential compares C as charging amboceptor, and using display₆Li current potential is high Current potential condensed aromatic compounds of group as electric discharge amboceptor, then can form the negative pole of mediator type.

Fig. 5 is the figure for representing to be used as the current potential of the condensed aromatic compounds of group of charging amboceptor 121.

Fig. 6 is the figure for representing to be used as the current potential of the condensed aromatic compounds of group of electric discharge amboceptor 122.

2 × 2cm copper foil is coated with the micro- porous barrier of polypropylene system, and by resulting material integrally with substantial amounts of lithium gold Belong to paper tinsel cladding.To copper foil and lithium metal installation collector plate.Then, layered product outer packing is installed.Inject thereto with Fig. 5 and Fig. 6 After shown each molar concentration (M) has dissolved the 2MeTHF of condensed aromatic compounds of group, will lamination in vitro package heat fusion from And seal.Thus for each condensed aromatic compounds of group, potential measurement element cell is made.Use is shown in Fig. 5 and Fig. 6 Current potential (the V vs.Li/Li that the potential measurement element cell is determined with lithium metal benchmark⁺).Furthermore can as ether in the measure Using 2MeTHF, but other ethers can also be used similarly.

Charging amboceptor 121 is without making C₆The ability of Li dissolvings in Li.On the other hand, electric discharge amboceptor 122, which has, makes C₆Li In Li dissolving ability.The capacity variance can be according to the current potential and C of their lithium metal solution₆For the difference of Li current potential It is bright.That is, C is compared₆Li current potential (about 0.2V vs.Li/Li⁺) it is high have make C₆The ability of Li dissolvings in Li.And compare C₆Li's Current potential (about 0.2V vs.Li/Li⁺) low without making C₆The ability of Li dissolvings in Li.

Therefore, it is possible to use compare C₆The low conduct charging amboceptor 121 of Li current potential.Further, it is possible to use compare C₆Li current potential High conduct electric discharge amboceptor 122.

Furthermore fewer with the potential difference of the 2nd active material 320 as condensed aromatic compounds of group, then charge-discharge energy is imitated Rate is more excellent.Therefore, graphite (C is being used₆Li, can be with as charging amboceptor 121 in the case of) being used as the 2nd active material 320 Use luxuriant and rich with fragrance, Sanya phenyl or biphenyl.In addition, as electric discharge amboceptor 122, cis-stilbene, phenyl propyl ketone, benzene pentanone can be used Or ethylenediamine.Thereby, it is possible to further improve charge-discharge energy efficiency.

Furthermore as ether, the ether not inserted together with Li ions in graphite can be used.Thus, ether will not insert together Graphite, it can further improve capacity density.

Furthermore as the 2nd active material 320, the active material (such as powdered active material) of solid can be used. In the case where the 2nd active material 320 is filled into tank with the pulverulence not being processed, manufacture can be simplified, And reduce manufacturing cost.

Or as the 2nd active material 320, the active matter of graininess (such as state by granulating powders) can be used Matter.By the 2nd active material 320 with particulate filler into tank in the case of, manufacture can be simplified, and reduce be manufactured into This.

Or as the 2nd active material 320, it can use by generally known adhesive (such as poly- inclined difluoro second Alkene, polypropylene, polyethylene, polyimides etc.) form granular active material.

Furthermore the 2nd active material 320 can be the material for being not dissolved in the 2nd liquid 120.Thereby, it is possible to realize that charging is situated between Body 121 and electric discharge amboceptor 122 circulate together with the 2nd liquid 120, but the liquid stream electricity of the structure that does not circulate of the 2nd active material 320 Pond.

Furthermore in the flow battery 3000 of embodiment 3, it is negative pole that can be set to the 2nd electrode 220, and the 1st electrode 210 be positive pole.

Furthermore as the side of the 1st electrode 210, if using the relatively low electrode structure of current potential, the side of the 2nd electrode 220 also may be used As positive pole.

I.e., it is possible to which it is positive pole to be set to the 2nd electrode 220, and the 1st electrode 210 is negative pole.

Furthermore contacted in the flow battery 3000 of embodiment 3, such as by the 2nd liquid 120 with the 2nd electrode 220, Charging amboceptor 121 and electric discharge amboceptor 122 are aoxidized or reduced by the 2nd electrode 220.That is, the activity of the 2nd liquid the 120 and the 2nd is for example passed through Material 320 contacts, so as to occur by the reduction reaction of 320 caused electric discharge amboceptor 122 of the 2nd active material or by the 2nd active matter The oxidation reaction of charging amboceptor 121 caused by matter 320.

2nd electrode 220 can be with the table to be played a role as charging amboceptor 121 and the reacting field of amboceptor 122 that discharges The electrode in face.

In this case, as the 2nd electrode 220, can be used for the stable material of the 2nd liquid 120 (such as insoluble in the 2nd The material of liquid 120).In addition, as the 2nd electrode 220, can be used for electrode reaction is the stable material of electrochemical reaction. For example, as the 2nd electrode 220, metal (stainless steel, iron, copper, nickel etc.), carbon etc. can be used.

2nd electrode 220 can be increase its surface area structure (such as silk screen, non-woven fabrics, surface roughening plate, Sintered porous bodies etc.).So increase the specific surface area of the 2nd electrode 220.Thereby, it is possible to more easily carry out the amboceptor 121 that charges With the oxidation reaction or reduction reaction of electric discharge amboceptor 122.

Furthermore the flow battery 3000 in embodiment 3 can be also equipped with the 2nd cycling mechanism 520.

2nd cycling mechanism 520 is the machine for making the 2nd liquid 120 be circulated between the 2nd electrode 220 and the 2nd active material 320 Structure.

Technological maheup more than, charging amboceptor 121 can be made and discharge amboceptor 122 together with the 2nd liquid 120 the Circulated between 2 electrodes 220 and the 2nd active material 320.Thereby, it is possible to the oxidation reaction being more effectively carried out between each material and Reduction reaction.

Mechanism of 2nd cycling mechanism 520 such as can be to possess pipe arrangement, tank, pump, valve.

As specific one of the 2nd cycling mechanism 520, structure of embodiment 4 described later etc. can be enumerated.

The explanation ＞ of ＜ charge and discharge process

Hereinafter, the charge and discharge process of the flow battery 3000 in embodiment 3 is illustrated.

Furthermore following technological maheups i.e. operational instances specifically, are exemplified, charge and discharge process is illustrated.

In addition, in this operational instances, the 2nd electrode 220 is negative pole, is set to stainless steel.

In addition, in this operational instances, the 2nd liquid 120 is set to the ether dissolved with charging amboceptor 121 and the amboceptor 122 that discharges Solution.

In addition, in this operational instances, the charging amboceptor 121 of the side of the 2nd electrode 220 is set to a kind of condensed aromatic compounds of group (being designated as ChMd below).

In addition, in this operational instances, the electric discharge amboceptor 122 of the side of the 2nd electrode 220 is set to a kind of condensed aromatic compounds of group (being designated as DchMd below).

In addition, in this operational instances, the 2nd active material 320 is set to graphite (C₆Li)。

In addition, in this operational instances, isolation part 400 is set to the solid electrolyte film of lithium ion conductive.

[explanation of charging process]

First, charging reaction is illustrated.

(reaction of negative side)

By the application of voltage, electronics is supplied from the outside of flow battery to the 2nd electrode 220 as negative pole.Thus, exist The reduction reaction of charging amboceptor 121 and the amboceptor 122 that discharges occurs on 2nd electrode 220.

For example, in this operational instances, following reactions occur.

ChMd+Li⁺+e^-→ChMd·Li

DchMd+Li⁺+e^-→DchMd·Li

By the 2nd cycling mechanism 520, make to move (supply) to setting by the charging amboceptor 121 that the 2nd electrode 220 reduces There is the place of the 2nd active material 320.

Now, the charging amboceptor 121 being reduced on the 2nd electrode 220, aoxidized by the 2nd active material 320.That is, the 2nd Active material 320 is electrically charged amboceptor 121 and reduced.Thus, the 2nd active material 320 absorbs lithium, turns into C₆Li。

For example, in this operational instances, following reactions occur.

6C+ChMd·Li→C₆Li+ChMd

By the 2nd cycling mechanism 520, make to move (supply) by the oxidized charging amboceptor 121 of the 2nd active material 320 and arrive It is provided with the place of the 2nd electrode 220.

As described above, from the point of view of charging amboceptor 121 is with the overall reaction including circulation, do not change.

On the other hand, being located remotely from the 2nd active material 320 in the place of the 2nd electrode 220 turns into charged state.

(reaction of side of the positive electrode)

For example, in this operational instances, following reactions occur.

TTF→TTF⁺+e^-

TTF⁺→TTF²⁺+e^-

For example, in this operational instances, following reactions occur.

LiFePO₄+TTF²⁺→FePO₄+Li⁺+TTF⁺

For example, in this operational instances, following reactions occur.

TTF⁺→TTF²⁺+e^-

On the other hand, being located remotely from the 1st active material 310 in the place of the 1st electrode 210 turns into charged state.

Charging reaction above, which may proceed to the 1st active material 310, turns into fully charged state or the 2nd active material Untill 320 turn into fully charged state.

[explanation of discharge process]

Then, the exoelectrical reaction since full charge is illustrated.

In full charge, the 1st active material 310 and the 2nd active material 320 turn into charged state.

(reaction of negative side)

By the electric discharge of battery, charging amboceptor 121 and the amboceptor 122 that discharges occur on the 2nd electrode 220 as negative pole Oxidation reaction.Thus, the outside release electronics from the 2nd electrode 220 to flow battery.

For example, in this operational instances, following reactions occur.

DchMd·Li→DchMd+Li⁺+e^-

ChMd·Li→ChMd+Li⁺+e^-

By the 2nd cycling mechanism 520, make to move (supply) to setting by the oxidized electric discharge amboceptor 122 of the 2nd electrode 220 There is the place of the 2nd active material 320.

Now, the electric discharge amboceptor 122 being oxidized on the 2nd electrode 220 is reduced by the 2nd active material 320.That is, the 2nd lives Property material 320 is discharged amboceptor 122 and aoxidized.Thus, the 2nd active material 320 discharges lithium.

For example, in this operational instances, following reactions occur.

C₆Li+DchMd→6C+DchMd·Li

By the 2nd cycling mechanism 520, make to move (supply) by the electric discharge amboceptor 122 that the 2nd active material 320 reduces and arrive It is provided with the place of the 2nd electrode 220.

As described above, from the point of view of electric discharge amboceptor 122 is with the overall reaction including circulation, do not change.

On the other hand, being located remotely from the 2nd active material 320 in the place of the 2nd electrode 220 turns into discharge condition.

(reaction of side of the positive electrode)

By the electric discharge of battery, electronics is supplied from the outside of flow battery to the 1st electrode 210 as positive pole.Thus, exist The reduction reaction of the 1st electrode amboceptor 111 occurs on 1st electrode 210.That is, in the surface of the 1st electrode 210, the 1st electrode amboceptor 111 It is reduced.

For example, in this operational instances, following reactions occur.

TTF²⁺+e^-→TTF⁺

TTF⁺+e^-→TTF

Now, the 1st electrode amboceptor 111 being reduced on the 1st electrode 210 is aoxidized by the 1st active material 310.That is, 1 active material 310 is reduced by the 1st electrode amboceptor 111.Thus, the 1st active material 310 absorbs lithium.

For example, in this operational instances, following reactions occur.

FePO₄+Li⁺+TTF→LiFePO₄+TTF⁺

For example, in this operational instances, following reactions occur.

TTF⁺+e^-→TTF

Exoelectrical reaction above, which may proceed to the 1st active material 310, turns into complete discharge condition or the 2nd active material Untill 320 turn into complete discharge condition.

The reckoning ＞ of ＜ energy densities

Hereinafter, the reckoning result of the energy density of the flow battery 3000 in embodiment 3 is illustrated.

Shown in Fig. 7 in the case where using each compound shown in above-mentioned Fig. 2 as the 1st electrode amboceptor 111, and Under conditions of the aforesaid operations example of flow battery 3000 in embodiment 3, and the amboceptor 121 that charges is luxuriant and rich with fragrance, electric discharge amboceptor The reckoning result of 122 energy density when being trans stilbene.

As shown in fig. 7, by using at 4,5 of tetrathiafulvalene skeleton and 4 ', 5 ' positions are bonded with the substituent of ring-type The Tetrathiafulvalene Derivatives of (electron-withdrawing substituent) as the 1st electrode amboceptor 111, can realize energy density for 654~ 672Wh/L or so flow battery.

On the other hand, the theoretical energy density of conventional flow battery (utilizing vanadium) is 38Wh/L or so.Can by the result Know, compared with conventional flow battery, the theoretical energy density of the flow battery of the disclosure is very high.

In addition, as shown in fig. 7, the tetrathiafulvalene of the substituent without ring-type is being used as the 1st electrode amboceptor 111 In the case of, form flow battery of the energy density for 633Wh/L or so.From the result, with using without ring-type The situation of the tetrathiafulvalene of substituent is compared, and uses the flow battery of the Tetrathiafulvalene Derivatives of the substituent with ring-type Theoretical energy density it is higher.

(embodiment 4)

Hereinafter, embodiment 4 is illustrated.Furthermore the appropriate any one weight omitted with above-mentioned embodiment 1~3 Multiple explanation.

Flow battery 4000 in embodiment 4, except the flow battery 3000 in above-mentioned embodiment 3 structure with Outside, following structures are also equipped with.

First, the flow battery 4000 in embodiment 4, possesses the 1st cycling mechanism shown in above-mentioned embodiment 2 510 structure.

In addition, the flow battery 4000 in embodiment 4, possesses the electrochemical reaction portion shown in above-mentioned embodiment 2 600th, positive terminal 211 and negative terminal 221.

In addition, the flow battery 4000 in embodiment 4 possesses the 2nd cycling mechanism 520.

2nd cycling mechanism 520 possesses the 2nd receiving portion 521.

2nd active material 320 and the 2nd liquid 120 are housed inside the 2nd receiving portion 521.

2nd cycling mechanism 520 makes the 2nd liquid 120 be circulated between the 2nd electrode 220 and the 2nd receiving portion 521.

The 2nd active material 320 contacts with the 2nd liquid 120 in the 2nd receiving portion 521, thus carries out by the 2nd active material The reduction reaction of the oxidation reaction of charging amboceptor 121 caused by 320 and the electric discharge amboceptor 122 caused by the 2nd active material 320 At least one of.

Technological maheup more than, can make the 2nd liquid 120 and the 2nd active material 320 in the 2nd receiving portion 521 Contact.Thus, such as the contact area of the 2nd liquid 120 and the 2nd active material 320 can be made bigger.In addition, the 2nd liquid can be made The time of contact of body 120 and the 2nd active material 320 is longer.Therefore, it is possible to be more effectively carried out being caused by the 2nd active material 320 The oxidation reaction of charging amboceptor 121 and the reduction reaction of the electric discharge amboceptor 122 caused by the 2nd active material 320.

Furthermore in embodiment 4, the 2nd receiving portion 521 for example can be tank.

In addition, the 2nd receiving portion 521 can for example accommodate to be dissolved with and fill in the gap for the 2nd active material 320 filled 2nd liquid 120 of dielectric 121 and electric discharge amboceptor 122.

In addition, as shown in figure 8, in the flow battery 4000 of embodiment 4, the 2nd cycling mechanism 520 can possess pipe arrangement 523rd, pipe arrangement 524 and pump 525.

One end of pipe arrangement 524 is with configuring one of the 2nd electrode 220 (shown in Fig. 8 among cathode chamber 610 and anode chamber 620 Example in be anode chamber 620) connection.

The other end of pipe arrangement 524 is connected with the inflow entrance side of the 2nd liquid 120 of the 2nd receiving portion 521.

One end of pipe arrangement 523 is connected with the flow export side of the 2nd liquid 120 of the 2nd receiving portion 521.

The other end of pipe arrangement 523 is with configuring one of the 2nd electrode 220 (in Fig. 8 institutes among cathode chamber 610 and anode chamber 620 It is anode chamber 620 in the example shown) connection.

Pump 525 is for example arranged at pipe arrangement 524.Or pump 525 can also be arranged at pipe arrangement 523.

Furthermore in the flow battery 4000 of embodiment 4, the 2nd cycling mechanism 520 can possess the 2nd and pass through suppressing portion 522。

2nd suppresses the transmission of the 2nd active material 320 through suppressing portion 522.

2nd is arranged at the path that the 2nd liquid 120 flows out from the 2nd receiving portion 521 to the 2nd electrode 220 through suppressing portion 522 (being pipe arrangement 523 in the example shown in Fig. 8).

Technological maheup more than, the 2nd active material 320 can be suppressed to (such as the 2nd electricity beyond the 2nd receiving portion 521 The side of pole 220) place outflow.That is, the 2nd active material 320 stays in the 2nd receiving portion 521.Thereby, it is possible to realize not make the 2nd activity The flow battery of the structure of material 320 circulation itself.Therefore, it is possible to prevent the part (such as pipe arrangement) of the 2nd cycling mechanism 520 Inside blocks caused by the 2nd active material 320.In addition, it can prevent because the 2nd active material 320 is to the side of the 2nd electrode 220 The generation of ohmic loss caused by outflow.

2nd passes through suppressing portion 522, such as can be arranged at the 2nd receiving portion 521 and the junction surface of pipe arrangement 523.

2nd transmission suppressing portion 522 for example can be the filter for filtering the 2nd active material 320.Now, filter can Be the particle with than the 2nd active material 320 the small hole of minimum grain size part.As the material of filter, can be used Not with the 2nd active material 320 and the material of the grade reaction of the 2nd liquid 120.Filter for example can be glass fiber filter paper, poly- third Alkene non-woven fabrics, not polyethylene nonwoven, the woven wire etc. with lithium metal reaction.

Technological maheup more than, even in the inside of the 2nd receiving portion 521, produced with the flowing of the 2nd liquid 120 The flowing of 2nd active material 320, also it can prevent the 2nd active material 320 from being flowed out from the 2nd receiving portion 521.

In the example shown in Fig. 8, the 2nd liquid 120 of the 2nd receiving portion 521 is contained in, the He of suppressing portion 522 is passed through from the 2nd Pipe arrangement 523 to anode chamber 620 by supplying.

Thus, the charging amboceptor 121 and electric discharge amboceptor 122 dissolved in the 2nd liquid 120 is aoxidized or gone back by the 2nd electrode 220 It is former.

Then, dissolved be oxidated or reduced charging amboceptor 121 and discharge amboceptor 122 the 2nd liquid 120, from Pipe 524 and pump 525 to the 2nd receiving portion 521 by supplying.

Accordingly, for the charging amboceptor 121 and electric discharge amboceptor 122 dissolved in the 2nd liquid 120, carry out by the 2nd active matter The reduction of the oxidation reaction of charging amboceptor 121 caused by matter 320 and the electric discharge amboceptor 122 caused by the 2nd active material 320 is anti- At least one of answer.

Furthermore the control of the circulation of the 2nd liquid 120 can for example be carried out by pump 525.That is, suitably carried out by pump 525 Beginning, the stopping of supply or the adjustment of quantity delivered etc. of the supply of 2nd liquid 120.

Or the 2nd the control of circulation of liquid 120 can be entered by the other means (such as valve etc.) different from pump 525 OK.

Furthermore it is in fig. 8, positive pole labeled as the 1st electrode 210 as one, and the 2nd electrode 220 is negative pole.

Here, if using the relatively low electrode structure of current potential as the side of the 1st electrode 210, the side of the 2nd electrode 220 also may be used With as positive pole.

Furthermore if the disclosure Tetrathiafulvalene Derivatives (at the 4 of tetrathiafulvalene skeleton, 5 and 4 ', 5 ' positions Be bonded with the Tetrathiafulvalene Derivatives of the substituent of ring-type), then with 4,5 of tetrathiafulvalene skeleton and 4 ', 5 ' position keys The Tetrathiafulvalene Derivatives for closing the substituent for having chain are compared, and can realize the energy with higher discharge potential and Geng Gao The flow battery of density.

Furthermore the structure that each single item of above-mentioned embodiment 1~4 is recorded, can suitably be mutually combined.

Industry utilizability

The flow battery of the disclosure can for example function well as electric energy storage device or accumulating system.

Description of reference numerals

110 the 1st liquid

111 the 1st electrode amboceptors

120 the 2nd liquid

121 charging amboceptors

122 electric discharge amboceptors

210 the 1st electrodes

211 positive terminals

220 the 2nd electrodes

221 negative terminals

310 the 1st active materials

320 the 2nd active materials

400 isolation parts

510 the 1st cycling mechanisms

511 the 1st receiving portions

512 the 1st pass through suppressing portion

520 the 2nd cycling mechanisms

521 the 2nd receiving portions

522 the 2nd pass through suppressing portion

600 electrochemical reaction portions

610 cathode chambers

620 anode chambers

1000th, 2000,3000,4000 flow battery

Claims

1. a kind of flow battery, possesses：

The 1st liquid dissolved with the 1st electrode amboceptor,

Be impregnated in the 1st liquid the 1st electrode,

Be impregnated in the 1st liquid the 1st active material and

The 1st cycling mechanism for making the 1st liquid be circulated between the 1st electrode and the 1st active material,

The 1st electrode amboceptor includes Tetrathiafulvalene Derivatives,

At 4,5 and 4 ' of the tetrathiafulvalene skeleton of the Tetrathiafulvalene Derivatives, 5 ' positions are bonded with ring style to be taken Dai Ji.

2. flow battery according to claim 1,

The Tetrathiafulvalene Derivatives are the Tetrathiafulvalene Derivatives represented by following formulas (1),

In formula (1), X is oxygen atom, sulphur atom, nitrogen-atoms, selenium atom or tellurium atom, also, R₁And R₂It is separately It is former selected from chain saturated hydrocarbons, chain unsaturated hydrocarbons, cyclic saturated hydrocarbon, ring-type unsaturated hydrocarbons, oxygen atom, sulphur atom, nitrogen-atoms, selenium It is at least one of sub, tellurium atom.

3. flow battery according to claim 2,

More than a kind electron withdraw group being bonded with the position of the X among sulphur atom, nitrogen-atoms, oxygen atom.

4. flow battery according to claim 2,

In the R₁With the R₂Position possess the substituent of straight-chain.

5. flow battery according to claim 2,

In the R₁With the R₂Position bonding substituent be C_nH_2n, n is the integer of satisfaction 1≤n≤4.

6. flow battery according to claim 2,

The Tetrathiafulvalene Derivatives are the Tetrathiafulvalene Derivatives represented by following formulas (2),

Wherein, R₃、R₄、R₅And R₆It is separately to be selected from chain saturated hydrocarbons, chain unsaturated hydrocarbons, cyclic saturated hydrocarbon, ring-type not Saturated hydrocarbons, oxygen atom, sulphur atom, nitrogen-atoms, selenium atom or tellurium atom at least one of.

7. flow battery according to claim 2,

In the R₁With the R₂Position bonding substituent include selected from boron, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, iodine it At least one of element.

8. flow battery according to claim 2,

The Tetrathiafulvalene Derivatives are that-bis- (sulphur of methylene two) tetrathiafulvalenes, 4,5,4 ', 5 '-are bis- selected from 4,5,4 ', 5 ' (ethylene sulphur) tetrathiafulvalene, 4,5,4 ', 5 '-bis- (sulphur of trimethylene two) tetrathiafulvalenes at least one of.

9. flow battery according to claim 1,

The Tetrathiafulvalene Derivatives have the 1st oxidation-reduction potential and the 2nd oxidation-reduction potential,

The equilibrium potential of 1st active material is higher than the 1st oxidation-reduction potential, and than the 2nd redox electricity Position is low.

10. flow battery according to claim 1,

1st cycling mechanism possesses the 1st receiving portion,

1st active material and the 1st liquid containing in the 1st receiving portion,

1st cycling mechanism makes the 1st liquid be circulated between the 1st electrode and the 1st receiving portion,

In the 1st receiving portion, the 1st active material contacts with the 1st liquid, thus carries out the 1st active matter At least one of oxidation reaction and reduction reaction between matter and the 1st electrode amboceptor.

11. flow battery according to claim 10,

1st cycling mechanism possesses the 1st that suppression the 1st active material passes through and passes through suppressing portion,

Described 1st is arranged on the 1st liquid from the road that the 1st receiving portion flows out to the 1st electrode through suppressing portion On footpath.

12. flow battery according to claim 1, is also equipped with：

The 2nd liquid dissolved with charging amboceptor and the amboceptor that discharges,

Be impregnated in the 2nd liquid the 2nd electrode,

Be impregnated in the 2nd liquid the 2nd active material and

The isolation part that will keep apart between 1st electrode and the 1st liquid and the 2nd electrode and the 2nd liquid,

The equilibrium potential of the charging amboceptor is lower than the equilibrium potential of the 2nd active material,

The equilibrium potential of the electric discharge amboceptor is higher than the equilibrium potential of the 2nd active material.

13. flow battery according to claim 12,

Lithium is dissolved with the 2nd liquid,

2nd active material is the material with the property for absorbing and discharging the lithium,

In charging, the charging amboceptor is reduced on the 2nd electrode, also, be reduced on the 2nd electrode The charging amboceptor is aoxidized by the 2nd active material, while the 2nd active material absorbs the lithium,

In electric discharge, occlusion has the 2nd active material of the lithium by the electric discharge mediator reduction, while the described 2nd is active Lithium described in substance release, also, the electric discharge amboceptor reduced by the 2nd active material on the 2nd electrode by oxygen Change.

14. flow battery according to claim 13,

In the charging, the electric discharge amboceptor is reduced on the 2nd electrode,

In the electric discharge, the charging amboceptor is oxidized on the 2nd electrode.

15. flow battery according to claim 12,

The charging amboceptor and the electric discharge amboceptor are condensed aromatic compounds of group,

The 2nd liquid dissolved with the condensed aromatic compounds of group, have release lithium solvated electron, by the lithium with The property of cationic form dissolving.

16. flow battery according to claim 15,

It is described charging amboceptor be selected from phenanthrene, biphenyl, ortho-terphenyl, Sanya phenyl, anthracene at least one of.

17. flow battery according to claim 15,

The electric discharge amboceptor is to be selected from phenanthroline, 2,2 '-bipyridyl, benzophenone, trans stilbene, 4,4 '-bipyridyl, 3, 3 '-bipyridyl, 2,4 '-bipyridyl, 2,3 '-bipyridyl, cis-stilbene, acetophenone, propiophenone, phenyl propyl ketone, benzene pentanone, second At least one of diamines.

18. flow battery according to claim 12,

The 2nd cycling mechanism is also equipped with, the 2nd cycling mechanism possesses the 2nd receiving portion,

2nd active material and the 2nd liquid containing in the 2nd receiving portion,

2nd cycling mechanism makes the 2nd liquid be circulated between the 2nd electrode and the 2nd receiving portion,

In the 2nd receiving portion, the 2nd active material contacts with the 2nd liquid, thus carries out living by the described 2nd Property the oxidation reaction of the charging amboceptor realized of material and pass through the electric discharge amboceptor that the 2nd active material is realized At least one of reduction reaction.

19. flow battery according to claim 18,

What the 2nd cycling mechanism possessed the transmission for suppressing the 2nd active material the 2nd passes through suppressing portion,

Described 2nd is arranged on the 2nd liquid from the road that the 2nd receiving portion flows out to the 2nd electrode through suppressing portion On footpath.